Langmuir 1996, 12, 1035-1039
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Characterization of Silk Crystallization Behavior on Highly Oriented Substrates Chao-Cheng Chen, Sophie Riou, and Shaw L. Hsu* Polymer Science and Engineering Department and Materials Research Science and Engineering Center, University of Massachusetts, Amherst, Massachusetts 01003
Howard D. Stidham Chemistry Department, University of Massachusetts, Amherst, Massachusetts 01003 Received June 16, 1995. In Final Form: October 17, 1995X Silk films cast from an aqueous solution onto oriented poly(tetrafluoroethylene) substrates and characterized by external reflection infrared spectroscopy showed that the oriented poly(tetrafluoroethylene) substrate both promoted crystallization of the silk II in a β-pleated sheet structure and induced orientation in the silk films, even for silk films cast from dilute silk solutions and salt solutions. Possible nucleation mechanisms are discussed.
Introduction The silk fibers produced by spiders and silkworms exhibit many impressive physical and mechanical properties, which has inspired numerous attempts to spin such fibers from silk solutions in vitro.1,2 It is particularly interesting that silk originates from an aqueous solution. In the spinning process water-soluble silk fibroin is converted at room temperature to insoluble high-performance fibers by a physical rather than chemical process. The only byproduct is water. The structure of silk can be quite complex. Bombyx mori cocoon silk is known to be composed of two proteins, fibroin and sericin. A double filament of fibroin is enveloped by an outer layer of sericin. Fibroin is the protein that gives silk its unique physical and chemical properties and consists of (Gly-Ala-Gly-Ala-Gly-Ser) repeating units in the crystalline regions. In these crystalline regions, the chain conformation has been established to be a planar β-pleated sheet packed in an antiparallel fashion, referred to as the silk II structure. The less stable water-soluble form is referred as silk I. Either silk I or II structures can be obtained from solution depending on the crystallization conditions. In the substantial silk literature dealing with the mechanism of crystallization, parameters such as solvent, concentration, temperature, drying rate, substrate, and so on are found to be important in determining the chain conformation of silk.1,3-5 Mechanical stress accompanying flow of the aqueous silk solution has been found to be particularly important in causing silk fibroin to precipitate into crystalline forms. On the basis of experiments on a steadystate flow of regenerated silk fibroin from Bombyx mori, Yamaura proposed that nucleation occurs in flow-induced oriented silk fibroin adsorbed to the solution surface.6 The * To whom correspondence should be sent. X Abstract published in Advance ACS Abstracts, February 1, 1996. (1) Magoshi, J.; Magoshi, Y.; Nakamura, S. In Silk Polymers; Kaplan, D., Adams, W. W., Farmer, B., Viney, C., Eds.; American Chemical Society: Washington, DC, 1994; p 292. (2) Asakura, T.; Yoshimizu, H.; Kakizaki, M. Biotechnol. Bioeng. 1990, 35, 511. (3) Ishida, M.; Asakura, T.; Yokoi, M.; Saito, H. Macromolecules 1990, 23, 88. (4) Magoshi, J.; Mizuide, M.; Magoshi, Y.; Takahashi, K.; Kubo, H.; Nakamura, S. J. Polym. Sci., Polym. Phys. Ed. 1979, 17, 515. (5) Magoshi, J.; Magoshi, Y.; Nakamura, S. J. Polym. Sci., Phys. Ed. 1981, 19, 185.
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oriented molecules associate to produce fibrillar crystals. Bombyx mori silk fibroin crystallizes to form fibers in solution. Iizuka showed that the critical shear rate for such crystallization changes with different ionic strength, pH, and fibroin concentration.7 It has also been found that growth of β-form spherulites can be promoted on the surface of well-oriented β-form silk filaments immersed in fibroin solution.8 These and earlier studies indicate that segmental orientation is crucial to the crystallization of β-form silk crystals from solutions of silk fibroin. Orientation of silk molecules can be accomplished by shearing silk fibroin solution6,7 or by adsorption to the air-water interface.9 In the present work, the influence of an oriented substrate on the crystallization of silk from an aqueous solution is investigated by casting a film of silk from solution onto a highly oriented poly(tetrafluoroethylene) substrate. Using such a substrate, oriented molecular crystals, polymers, or even certain inorganic materials can be formed from the melt, from the solution, or from the vapor.10-12 Vibrational spectroscopy is used in this work to characterize silk films. When bands are properly assigned and the polarization state is well defined, vibrational spectroscopy provides a measure of structures at the localized level. Indeed, transmission infrared spectroscopy has been used to characterize silk films since the early 1950s and this pioneering work served to establish many assignments and band polarizations.13 Transmission spectroscopy is not well suited to the present work, however, as the strong infrared absorptions of the poly(tetrafluoroethylene) substrate are expected to obscure the spectrum of the thin silk films formed at the polymer surface. For this reason, external reflection infrared spectroscopy was chosen to characterize both the micro(6) Yamaura, K.; Okumura, Y.; Matsuzawa, S. J. Macromol. Sci., Phys. 1982, B21, 49. (7) Iizuka, E. J. Appl. Polym. Sci.: Appl. Polym. Symp. 1985, 41, 173. (8) Magoshi, J. Polymer 1977, 18, 643. (9) Muller, W. S.; Samuelson, L. A.; Fossey, S. A.; Kaplan, D. Langmuir 1993, 9, 1857. (10) Wittman, J. C.; Smith, P. Nature 1991, 352, 414. (11) Hansma, H.; Motamedi, F.; Smith, P.; Hansma, P.; Wittman, J. C. Polymer 1992, 33, 647. (12) Fenwick, D.; Ihn, K. J.; Motamedi, F.; Wittman, J. C.; Smith, P. J. Appl. Polym. Sci. 1993, 50, 1151. (13) Bamford, C. H.; Elliot, A.; Hanby, W. E. In Synthetic Polypeptides: Preparation, Structure and Properties, 1st ed.; Academic Press, Inc.: New York, 1956; Vol. 5, Chapter 12.
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structure of the substrate and that of the silk crystals formed. This reflectance technique has been shown to be an effective technique to characterize polymer structure adsorbed onto dielectric substrates.14 The oriented poly(tetrafluoroethylene) surface proved able to induce crystallization. The results obtained in the present investigation are reported here. Experimental Section Silk cocoon was degummed by boiling in deionized water with sodium dodecyl sulfate (0.5%). Degummed silk was then dissolved in aqueous 9.3 M LiBr solution. The solution was dialyzed against deionized water for 72 h with 12 000-14 000 MW cut-off Spectrapor membrane. The water was changed every 24 h. Rapid transport to LiBr to the dialysate was established via conductivity measurements of the silk solutions. The dialyzed solution was then filtered with 0.45 mm Millipore filters. All silk solutions were stored at 5 °C. We used a solution concentration of 0.5 g/L (or 0.05%). The procedure used to prepare a smooth, highly oriented substrate followed the one described by Wittman et al.10 and involved rubbing one face of a commercial grade, melt-crystallized poly(tetrafluoroethylene) block back and forth four times on a glass microscopy slide at a controlled temperature (300 °C) and pressure (40 N/cm2). The film thickness of the friction-transferred poly(tetrafluoroethylene) polymer film was measured with a Zygo optical phase interference microscope Maxim3D 5800. The smaller magnification lens, 20×, provides a vertical resolution of ∼1 Å and a lateral resolution of ∼1 µm. A typical film thickness measured by the Zygo apparatus is around 950 Å. The thin poly(tetrafluoroethylene) films can be lifted from the glass by immersion in water. Copper grids (300 mesh) were then used to pick up the films from the water surface; the films were then air-dried and examined with a JEOL 100 CX instrument operated at 100 kV. The sample-film distance was calibrated with sputtered thin gold films. Silk fibroin films were cast onto bare or oriented poly(tetrafluoroethylene)-coated glass slides from a silk solution (0.05%) at room temperature and then dried in vacuum. To cast films from the 9.3 M LiBr silk solution (0.05% silk), the solution on the substrates was first equilibrated for 2 days with a saturated aqueous solution of LiBr. Silk fibroin then deposits on the substrates without coprecipitation of LiBr crystals. The glass slides were rinsed with deionized water for 1 min and quickly dried in a stream of dry air. Reflectance spectra were obtained with a Perkin-Elmer 2000 FTIR spectrometer equipped with wide and narrow band mercury-cadmium-telluride (MCT) detectors, using an external reflection cell purchased from Graesby Specac in Waterbury, CT. The incident angle was chosen at 30° relative to the surface normal.14 The reflectance spectrum is defined as -log(R/R0), where R0 is the reflectivity of a bare glass, and R is the reflectivity of a film deposited on glass. In general, the intensity of a reflectance spectrum depends on the polarization state of the incident radiation, the angle of incidence, and the thickness of the films being studied.14 Since in this experiment only the inplane orientation of poly(tetrafluoroethylene) and silk fibroin on glass slides is of interest, only s polarization (the electric vector of the incident light perpendicular to the scattering plane defined by the incident and exit radiation) was used. A gold-grid polarizer was placed immediately before the glass sample. To probe the molecular orientation characteristics of poly(tetrafluoroethylene) or silk fibroin, the glass slide was rotated relative to the polarizer by 90°. In this study, the parallel and perpendicular spectra are defined by orienting the incident polarization parallel and perpendicular to the rubbing direction. For isotropic films on glass, the rotation was found to produce minimal changes in the spectrum. There are several bands associated with the amide group which can be used to characterize chain conformation and packing. For example the amide I bands are found at 1660, 1645, and 1630 cm-1 for R, disordered, and β structures, respectively. The bands observed for silk films prepared often exhibit asymmetric broad band shapes suggesting multiple structures. Band deconvolution (14) Ren, Y. Ph. D. Thesis, U. Massachusetts, 1995.
Figure 1. Reflectance infrared spectra of a friction-deposited poly(tetrafluoroethylene) film on a glass slide, with the infrared beam polarized parallel and perpendicular to the rubbing direction. (Lab Calc) was used to assess quantitatively the amount of each component. The 1710-1600 and 1600-1500 cm-1 regions were each deconvoluted into three contributions. A combination of Gaussian and Lorentzian band shapes was used. Frequency, width at half-height, intensity, and percentage of Gaussian or Lorentzian band contribution to the contour were varied to obtain the best fit.
Results and Discussion The external infrared reflection spectra of a frictiondeposited poly(tetrafluoroethylene) film is displayed in Figure 1. Bands at 637, 1150, and 1210 cm-1 are characteristic of a 157 helical chain conformation, and the 624 cm-1 band is a defect band.15,16 These spectra were obtained using s polarization with the electric vector of the light incident on the polymer surface oriented either along or perpendicular to the rub direction, depending on the sample orientation. The different signs of the absorbance for those bands with different polarization characteristics can only be understood if poly(tetrafluoroethylene) chains lie parallel to the film surface.14 The spectra shown in Figure 1 suggest that the segmental orientation along the rubbing direction in the poly(tetrafluoroethylene) film deposited on glass slides seems to be extremely high. The orientation function estimated from the dichroic ratio for the 1210 cm-1 band is 0.62, which is comparable to the plateau value found in mechanically drawn bulk poly(tetrafluoroethylene).17 Even though the crystalline chains are highly oriented, the 850 cm-1 band assigned to the amorphous structure18 exhibits no orientation. To further ascertain whether the deposited thin film of poly(tetrafluoroethylene) has the same crystalline structure as conventional bulk material, electron diffraction experiments were conducted. Typical results are shown in Figure 2. The diffraction patterns obtained indicate a highly oriented structure, and a number of high-order spots are observed. When the sample is rotated around the rubbing direction, extra diffraction spots become apparent at 30° and 60°. This is an indication that the sample has a hexagonal unit cell and that close-packed poly(tetrafluoroethylene) 100 crystalline planes are parallel to the substrate. Unit cell dimensions were calculated (15) Masetti, G.; Cabassi, F.; Morelli, G.; Zerbi, G. Macromolecules 1973, 6, 700. (16) Zerbi, G.; Sacchi, M. Macromolecules 1973, 6, 692. (17) Davidson, T.; Gounder, R. N. In Adhesion and Adsorption of Polymers; L. H., Lee, Ed.; Plenum Press: New York, 1980; Vol. 12B, p 775. (18) Moynihan, R. E. J. Am. Chem. Soc. 1959, 81, 1045.
Silk Crystallization Behavior
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Figure 3. Reflectance infrared spectra of silk films cast from an aqueous silk solution onto different substrates.
Figure 2. Electron diffraction patterns of a friction-deposited poly(tetrafluoroethylene) film: (a) electron beam normal to the film and (b) film tilted around the rubbing direction.
using equatorial and meridian diffraction. The intermolecular spacing is calculated to be 5.31 Å, and the chain repeat of the 15 CF2 groups is 19.8 Å. These measurements compare modestly well with the values of 5.55 and 19.5 Å reported by Bunn et al.19 These results are consistent with a 157 helical chain phase IV structure which exists between 19 and 35 °C for bulk material.19,20 These data indicate that the rub-deposited thin film poly(tetrafluoroethylene) has the same structure as the crystalline bulk material and that their molecules lie on the surface of the glass slide with a preferred segmental orientation parallel to the rubbing direction. To describe quantitatively the amount of various crystallites formed, it is important to remove the polarization characteristics of the spectra obtained. Therefore, the average of the two polarized spectra obtained for the incident polarization parallel and perpendicular to the rubbing direction is shown in Figure 3 for a silk film cast onto an oriented poly(tetrafluoroethylene) substrate and compared with isotropic silk films, e.g., films cast onto glass slides or unoriented poly(tetrafluoroethylene). The isotropic films do not require this treatment since the individual polarized spectra are the same in all directions. Two polarized spectra obtained for the film cast from dilute solution (0.5 g/L) onto an oriented poly(tetrafluoroethylene) surface, shown in Figure 4, are used to calculate the (19) Bunn, C. W.; Howells, E. R. Nature 1954, 174, 549. (20) Sperati, C. A.; Starkweather, H. W. Adv. Polym. Sci. 1961, 2, 465.
Figure 4. Reflectance infrared spectra of a silk film cast from an aqueous silk solution onto an oriented poly(tetrafluoroethylene) surface, with the infrared beam polarized parallel and perpendicular to the rubbing direction.
average spectrum. The amide I and II bands near 1650 and 1520 cm-1 exhibit multiple components. The amide I band has a sharp maximum near 1623 cm-1 in all three spectra, and there are two more components at higher frequencies, near 1690 (weak) and 1655 cm-1. The amide II band in the lower frequency region also has two principal components, a sharp feature centered at about 1522 cm-1 and a broader weaker component near 1540 cm-1. The amide I and II vibrations at 1623 and 1522 cm-1, respectively, have long been recognized as being due to out-of-phase vibrations of adjacent amide groups involved in an antiparallel β-pleated sheet, giving rise to a transition moment perpendicular to the chain direction.21 The weak band at about 1690 cm-1 does not always occur in crystalline protein (it is missing in the spectrum of β-keratin) and was assigned by Miyazawa as the amide I vibration in which adjacent groups in an antiparallel β-pleated sheet move in phase with one another,21 giving rise to a transition moment parallel to the chain direction. The splitting between the in-phase and out-of-phase vibrations has been accounted for by including a transition dipole coupling between adjacent groups.21-24 The amide I and II bands at 1655 and 1540 cm-1, respectively, are characteristic of disordered structures. The film cast onto an oriented poly(tetrafluoroethylene) substrate has a larger crystalline (silk II) content. Band deconvolution suggested that the amount of silk II (21) Miyazawa, T.; Blout, E. R. J. Am. Chem. Soc. 1961, 83, 712. (22) Miyazawa, T. J. Chem. Phys. 1960, 32, 1647. (23) Moore, W. H.; Krimm, S. Biopolymers 1976, 15, 2465. (24) Abe, Y.; Krimm, S. Biopolymers 1972, 11, 1817.
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Figure 5. Reflectance infrared spectra of silk films cast from an aqueous LiBr/silk solution onto different substrates.
structure in the film cast onto oriented poly(tetrafluoroethylene) is approximately 55%, while that for the film cast onto glass is only about 30%. All samples contained a significant amount of disordered structure but not more so than native fibers. Magoshi et al. found that films cast from solutions with concentrations less than 3% have predominantly disordered structures.25 The amount of disordered structure is slightly larger in the film cast onto an unoriented poly(tetrafluoroethylene) surface than onto glass, consistent with the observation of Magoshi et al.25 that silk films cast onto hydrophobic substrates have more disordered structure than films cast onto hydrophilic substrates. Polarized external reflectance infrared spectra obtained for films cast from a dilute aqueous solution (0.5 g/L) onto an oriented poly(tetrafluoroethylene) film are shown in Figure 4. The relative intensities are quite different for the two polarizations. The 1623 cm-1 band has the highest intensity when the rubbing direction is perpendicular to the infrared beam polarization direction. This suggests that the silk II structure has a preferred segmental orientation along the rubbing direction, i.e., parallel to the orientation of poly(tetrafluoroethylene) molecules. Deconvolution of the amide I region shows that the disordered band has much less dichroism. Figure 5 compares the spectra obtained for films cast from an aqueous LiBr/silk solution onto an oriented poly(tetrafluoroethylene), onto an unoriented poly(tetrafluoroethylene), and onto glass. The most intense band is broad and centered at 1630 cm-1, some 5-7 wavenumbers higher than the most intense band in the spectrum of the film cast from the salt-free solution, indicating silk II crystallization with a wider distribution of chain conformation in the film cast from the LiBr solution. All three samples shown in Figure 5 have a broad band at 1660 cm-1. This band is diagnostic for disordered chain conformations and entirely dominates the spectra of the film cast onto unoriented poly(tetrafluoroethylene) and onto glass. Band deconvolution suggests that the film cast from the LiBr solution onto oriented poly(tetrafluoroethylene) has about 51% β-chain conformation. The broad amide II band maxima are at 1530-1540 cm-1 for the different samples. The lower frequency is found for the sample with the highest crystallinity, the higher for the samples with less crystallinity. These results show that the oriented poly(tetrafluoroethylene) surface has the ability to nucleate the silk II structure for films cast from LiBr solution, even though silk fibroin molecules assume a more contracted and disordered conformation (25) Magoshi, J.; Kamiyama, S.; Nakamura, S. Proc. 7th Int. Wool Textile Res. Conf. 1985, 1, 337.
Chen et al.
Figure 6. Reflectance infrared spectra of a silk film cast from an aqueous LiBr/silk solution onto an oriented poly(tetrafluoroethylene) surface, with the infrared beam polarized parallel and perpendicular to the rubbing direction.
than found in salt-free solution.26 The spectra of the film cast from the aqueous LiBr/silk solution onto oriented poly(tetrafluoroethylene) are shown in parallel and perpendicular polarization in Figure 6. Comparison of Figures 4 and 6 shows an especially interesting phenomenon: in Figure 4, the greatest intensity of the 1623 cm-1 band is found when the electric vector of the incident infrared light is oriented perpendicular to the rubbing direction of the oriented poly(tetrafluoroethylene), while in Figure 6, the greatest intensity of the 1630 cm-1 band occurs when the orientation is parallel. Apparently, the crystalline segmental orientation of the film cast from the salt-free solution is orthogonal to that of the film obtained from the salt solution, a startling result. The mechanism for the enhanced crystallization of specific forms of silk II on oriented poly(tetrafluoroethylene) is not entirely clear. Epitaxial crystallization might explain the orientation in films cast from salt-free aqueous solution, since the mismatch between the intermolecular spacing (or atomic spacing along the chain axis) of poly(tetrafluoroethylene) and that of silk fibroin molecules is only about 11%, within the usually accepted range of spacing mismatches that allows epitaxial crystallization.27 Takahashi attributed the alignment tendency of nylon 6, polyethylene, or polycaprolactone crystals grown from the melt on drawn poly(tetrafluoroethylene) to epitaxial crystallographic interaction with similarity of atomic spacing along the chain axes of deposit and substrate polymers.28 However, lattice match does not preclude epitaxial control through surface topography. Therefore, the surface topography may provide another possible mechanism (grapho epitaxy). The surface shows hollow ditches aligned with the rubbing direction, with lateral dimensions varying from more than 5 nm to less than 1 µm.11 Polymer molecules adsorbed in these ditches perhaps can be forced to assume a stretched conformation over some distance, possibly facilitating nucleation of the silk II structure.29 On the basis of the oriented crystallization of polyethylene on various alkali halides and also that of different polymers on sodium chloride, it has also been concluded that lattice matching with the substrate may not be important. The preferential chain orientation of polyethylene was observed in the 〈110〉 directions of the halide crystals. In that case, the epitaxial mechanism (26) Iizuka, E.; Yang, J. T. Biochemistry 1968, 7, 2218. (27) Wittmann, J. C.; Lotz, B. J. Polym. Sci., Polym. Phys. Ed. 1981, 19, 1837. (28) Takahashi, T.; Teraoka, F.; Tsujimoto, I. J. Macromol. Sci., Phys. 1976, B12, 303. (29) Binsbergen, F. L. Polymer 1970, 11, 253.
Silk Crystallization Behavior
has been attributed to the long range dipolar forces exerted by rows of like-charged ions on these surfaces.30 It is possible that in films deposited from LiBr solution the chain conformation is distorted by interaction of the peptide groups with Li+ ions. The distortion of the transition dipole coupling between adjacent peptide residues may cause a decrease in the band splitting in both the amide I and II bands. In other words, these vibrations would move closer to the uncoupled vibrational states at higher frequencies.31 Complex formation between lithium ions and amide groups in systems containing LiBr and polypeptides or simple amides has been proposed to explain the observed changes in vibrational spectra,32-35 and the explanation may apply here as well. Formation of a new crystallographic structure as a result of interaction with the salt for fibrous proteins immersed in highly concentrated LiBr aqueous solutions has also been postulated.35 Infrared spectral shifts in amide I and II regions similar to the present study were also observed for nylon 6-inorganic salt mixtures.36 The unexpected orientation observed for the LiBr-silk crystals formed on the oriented poly(tetrafluoroethylene) film cannot be explained easily. It is clear that cross β-crystals can form in polypeptides and silk.26,37,38 In those cases, the extended polypeptide chain segments are oriented perpendicular to the fiber axis. Infrared spectra obtained for those samples show that the CdO and NH (30) Koutsky, J. A.; Walton, A. G.; Baer, E. J. Polym. Sci. A-2 1966, 4, 611. (31) Chirgadze, Y. N.; Shestopalov, B. V.; Venyaminov, S. Y. Biopolymers 1973, 12, 1337. (32) Baddiel, C. B.; Chaudhuri, D.; Stace, B. C. Biopolymers 1971, 10, 1169. (33) Balasubramanian, D.; Shaikh, R. Biopolymers 1973, 12, 1639. (34) Kurtz, J.; Harrington, W. F. J. Mol. Biol. 1966, 17, 440. (35) Mandelkern, L.; Halpin, J. C.; Diorio, A. F.; Posner, A. S. J. Am. Chem. Soc. 1962, 84, 1383. (36) Kim, H.; Harget, P. J. J. Appl. Phys. 1979, 50, 6072. (37) Anderson, J. M.; Chen, H. H.; Rippon, W. B.; Walton, A. G. J. Mol. Biol. 1972, 67, 459. (38) Bradbury, E. M.; Brown, L.; Downie, A. R.; Elliott, A.; Fraser, R. D. B.; Hanby, W. E.; McDonald, T. R. R. J. Mol. Biol. 1960, 2, 276.
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bonds of the peptide group are aligned along the direction of stroking. The diffraction spacing and infrared frequency measured for the amide vibrations are characteristic of the β-structure. Possibly, crystals of a complex with LiBr form from silk/LiBr solution that are then accommodated into the ditches associated with the friction-transferred poly(tetrafluoroethylene) film.11 The different crystallization behavior of silk films cast from salt-free solution and LiBr-containing solution in these ditches could be due to the fact that silk molecules in solution assume a more contracted conformation in the presence of a high concentration of LiBr than in salt-free solution.26 The more compact conformation would favor intramolecular interaction enhancing nucleation in the ditches with folded-chain structures oriented along the rubbing direction. Conclusions Highly oriented poly(tetrafluoroethylene) films were obtained by rubbing a poly(tetrafluoroethylene) block on glass slides under pressure and at a suitable temperature. Silk films cast from either an aqueous silk solution or an aqueous silk-LiBr solution onto the oriented poly(tetrafluoroethylene) surface exhibit more silk II structure than those cast either onto glass slides or onto unoriented poly(tetrafluoroethylene) surfaces under the same conditions; the silk II crystals show preferred segmental orientation along or perpendicular to the oriented poly(tetrafluoroethylene) molecules, respectively. Therefore, oriented poly(tetrafluoroethylene) films can be used as templates to control the cast film structures and their orienting ability is ascribed to epitaxial lattice matching between substrate and deposit polymers and also to the specific surface topography. Acknowledgment. This research has been supported by a grant from the NSF Materials Research Science and Engineering Center. LA950491E
